omega-perfluoroalkyl alkenols



United States Patent 3,285,975 w-PERFLUOROALKYL ALKENOLS Arthur H.Ahlbrecht, Dellwood, Minn., assignor to Minnesota Mining andManufacturing Company, St. Paul, Minn., a corporation of Delaware NoDrawing. Filed Mar. 1, 1965, Ser. No. 436,281 3 Claims. (Cl. 260633)This application is a continuation-in-part of the copending applicationSerial No. 247,357 filed on December 26, 1962, now US. Patent 3,171,861,which is in turn a continuation-in-part of two earlier filed co-pendingapplications, Serial Nos. 664,911 filed June 11, 1957, now US. Patent3,128,272 and 677,229 filed August 9, 1957, now abandoned.

This invention relates to a novel and useful class of fiuorinatedaliphatic alcohols and to a process for the production of fiuorinatedaliphatic alcohols.

It is an object of this invention to provide a novel class offluorocarbon alkanols which have a variety of uses as chemicalintermediates. Another object of the invention is to provide a processfor the preparation of perfiuoroalkyl alcohols which are intermediatesin the preparation of perfluoroalkyl acrylates and polymers thereof.Another object of the invention is to provide a process for thepreparation of a class of intermediates in the preparation of certainperfluoroalkyl-substituted triazines and condensation products thereofwith formaldehyde. Another'object of the invention is to provideintermediates in the preparation of certain perfiuoroalkyl-substitutedhalomethyl ethers and quarternary amine salt derivatives thereof. Stillanother object of the present invention is to provide intermediates inthe preparation of certain carbamates. A further object of the inventionis to provide intermediates in the preparation of certainperfiuoroalkylsubstituted textile treatments. A further object of theinvention is to provide intermediates in the preparation ofthermosetting polymers possessing both oil and water repellentcharacteristics. A further object of the invention is to provideintermediates in the preparation of surface coating compositions ofenhanced oil and water repellent characteristics. A furtherobject of theinvention is to provide a process for the preparation of certainperfluoroalkyl alcohols. Other objects of the invention will becomeapparent from the following specification.

The fluorocarbon alkenols of the invention can be represented by thegeneral formula:

R;CH= CH CH OH wherein R is a perfluoroalkyl group having from 3 to 12carbon atoms and n is 0-10, preferably 1-10.

The process of the invention can be represented by the followingstructural steps:

wherein R and n are as previously defined, m is n+2, X is halogen otherthan fluorine (bromine, chlorine .or iodine), R is hydrogen or and R islower alkyl (ordinarily butyl or lower). Preferably in the products andprocess of the invention 12 is at least 1.

Thus when R is hydrogen, the process involves a dehydrohalogenation stepand a hydrogenation step. When R is the ester residue it also involvessaponification-replacing the with H. Depending upon the conditionsselected at can be isolated. Thus the alcohols of the invention areproducts of the first step of the process of the invention and areintermediates in the preparation of the saturated alcohols which areproduced by the hydrogenation. The dehydrohalogenation can beconveniently carried out .by treating the halogenated precursor withsodium methylate or other similar reagent. The unsaturated intermediatecan then be hydrogenated, for instance, by dissolving it together withan excess of an alkali metal hydroxide in a solvent (eg a loweraliphatic alcohol or a mixture of water and a lower aliphatic alcohol)and subjecting the solution to hydrogen at a relatively high pressure(e.g. 500 to 5000 p.s.i.) in the presence of a hydrogenation catalystsuch as Raney nickel. Preferably, this is done at a temperature of 200C. although lower or higher temperatures can be used.

The dehydrohalogenation and hydrogenation steps of the process can alsobe carried out together, e.g. by subjecting the halogenated precursor tohydrogen at a relatively high pressure in the presence of Raney nickelunder basic conditions as previously disclosed. These variations areconsidered to be within the scopeof the process of the invention, asrepresented above.

The precursor halogenated alcohols and esters of'the process of theinvention are available by desulfonylatively reacting aperfiuoroalkanesulfonyl chloride, a perfluoroalkanesulfonyl bromide or aperfluoroalkyl iodide with a distally unsaturated alkenol or an esterthereof. The precursor halogenated alcohols can also be prepared bysaponification of the corresponding halogenated esters.

The fiuorinated alcohols prepared by the process of the invention whichcontain a plurality of methylene groups but not more than 12 such groupsbetween a perfluoroalkyl radical having from 3 to 12 carbon atoms andthe hydroxyl group can be prepared by various methods, e.g.

catalyst RrSOgCl CHz=CH(CH2)l-1DOH RrOHzOHCKCHDl-mO catalyst E11CHz=CH(CHg)1-1oOI1 a RgCHqCHHCHzh-roOH catalyst R1SOgC1+ CHz=CH(CHz)-nCOzH RrCHgCHCKCHgh-nCOzH catalyst B15020]. OHz=OH(CHa)1-C 01R Hg,copper RK(OHZ) 4-1203: Rt(CH2)3-11C 02 chromite catalyst [I H,, RaneyNickel, KOH

RICHICHI(CH2)1IC OzH Raney Nickel H RrSOgCl CH1=CH(CHz) oOCRRiCH2CHC1(CHl)1-IOOCR LiAlH 1(C 2)suOH A number of the unsaturatedalcohols of the invention and the corresponding saturated alcoholsproduced by the process of the invention are given in the followingtable:

Unsaturated alcohol Saturated alcohol 3-(perfluorobutyl)propanol-l.3-(perfiuorooctyl) propanol-l. 3-(perfluorododecyl)propanol-l.4-(perfiuorooetyl) butanol-l. 5-(perfluoropropyl)pentanol-l.5-(perfiuorobutyl)pentanol'l. 5-(perfiuorooetyl) pentanol-l.5-(perlluorododeeyl) pentanol-l. 6-(perfluorodecyl)hexanol-1.7-(pertluorocctyl)heptanoH. S-(perfluorobutyl)octanol-l.S-(perfluorooctyl)oetanol-l. E-(perfluorododecyl) oetanollll-(perfiuorobutyl)undecanol-l. ll-(perfiuorooctyDundecanol-l.ll-(perfiuorododeeyl) undecanol-l.

The saturated alcohols produced by the process of the present inventionare extremely valuable and versatile as chemical intermediates. Amongthe classes of materials which can be prepared from them are:

A. Acrylate-type esters and polymers thereof.

B. Triazines carrying an w-perfiuoroalkyl group and condensationproducts thereof with formaldehyde.

C. w-Perfluoroalkyl halomethyl ethers'and quaternary amine saltsthereof.

D. Carbamates produced by reaction of isocyanates with the alcohols ofthis invention.

A. The acrylate-type esters are prepared by esterifying the saturatedalcohols with acrylic acid or methacrylic acid. These esters have thegeneral formula:

wherein R; and m are as previously defined herein and R" is hydrogen ormethyl. These monomers are readily polymerized by methods known to theart, for example, by bulk polymerization, solution polymerization andemulsion polymerization, using catalysts such as benzoyl peroxide orother free radical polymerization initiators. The resulting polymers,including both homopolymers and co polymers, are characterized by thepresence in the skeletal chain of repetitive or recurring units whichcan be represented as follows:

CH: O

When fibers are coated with these polymers, oil and water resistance areimparted to the fibers Whether in the form of a woven fabric or cloth,or in the form of a random web as in paper or felt.

B. The triazines which are produced from the saturated alcohols have thegeneral formula wherein R and m are as previously defined herein and Yand Z are amino or hydrazino radicals. These triazines are prepared bycondensing an alcohol according to the present invention with amono-halogenated triazine derivative, for example, with2,4-diamino-6-chloro-s-triazine (formed by partial reaction ofcommercially available cyanuric chloride with ammonia, as described inthe J ournal of the American Chemical Society, vol. 73, pages2981-2983). The 2,4 dihydrazino 6-(w-perfiuoroalkyl alkyloxy)-s-triazines are prepared by reacting a saturated alcohol producedby the process of the invention with cyanuric chloride and by thenreacting the two remaining chlorine atoms on the triazine nucleus withhydrazine.

The perfluoroalkyl group-containing triazines are useful intermediatesfor the preparation of polymeric substances by condensation withformaldehyde. The polymeric materials thus produced are thermosettingresins which exhibit oil and water repellent characteristics. They canbe cast in the form of thin sheets or films which have these properties,or they can be employed as coatings; for example on fibrous substratessuch as paper, textiles such as cotton, wool, linen, silk and syntheticfibers, non-woven mats or webs of fibers and felt.

Additionally, the substituted triazines can be used as curing agents forepoxy resins, whereby the cured resins have increased oil and waterrepellency. The formaldehyde condensation products can be convenientlyproduced by refluxing together for from one to four hours concentratedaqueous formaldehyde and the perfluoroalkyl group-containing triazine.

C. The saturated alcohols are also useful as intermediates in thepreparation of halomethyl ethers of the type:

R (CH OCH D wherein D is chlorine or bromine. The compounds in turn canbe reacted to form quaternary amine salts of the type:

f( 2)m 2Q wherein Q is the radical of a tertiary nitrogenous base. Thehalomethyl ethers are prepared by reaction of formaldehyde and hydrogenhalide, e.g., hydrogen bromide or hydrogen chloride, with thecorresponding fluorinated alcohol to produce a halomethyl ether, whichis not necessarily isolated when quaternization is to be effected, butis readily quaternized directly by addition of a tertiary amine such aspyridine. This procedure is conveniently carried out by passing theselected anhydrous hydrogen halide in gaseous form into a. solution ofthe alcohol and paraformaldehyde in an inertsolvent, such as toluene,benzene and the like until there is substantially no further absorptionof the hydrogen halide. As the reaction is not strongly exothermic, notemperature control is required, although heating from about 25 C. to100 C. (depending to an extent on the boiling point of the solvent used)may be resorted to, to insure completion of the reaction. Anotherprocedure which is very convenient since it avoids the use of hydrogenhalide is to react the alcohol and paraformaldehyde with the hydrohalideof the tertiary nitrogenous base, e.g., pyridine hydrochloride, in asuitable solvent such as the base. Isolation of the quaternary salt isthen carried out as above adding, if desired, a further amount of anorganic solvent such as, e.g., ether. The two procedures are to beconsidered equivalent.

Without isolation of the intermediate halomethyl ether,

'quaternization' is efiected in the inert solvent employed for theprevious reaction after brief evaporation to remove excess hydrogenhalide, or the reaction mixture may be further evaporated and some othersolvent, such as anhydrous ether or dioxane, in which the quaternarysalt is insoluble, may be added. The desired tertiary organic base oramine is then added in the stoiohiometric amount while maintaining thereaction mixture at a temperature in the range of about 25 C. to about100 C. Any tertiary nitrogenous organic base which is capable of forminga salt or quaternary compound is suitable for this purpose, including,for example, trialkyl amines, such as trimethylamine, tributylamine andtridodecylamines; cycloalkyl amines such as tricyclohexylamine; arylalkyl amines such as benzyl dimethyl amine; alkarylamines such asdimethyl aniline; and heterocyclic amines as pyridine, picoline,lutidine, quinoline, and the like. Pyridine is particularly preferredfor convenience and economy in formation of cloth-treating agents asshown above.

These quaternized compounds are employed for treating woven or non-Wovenfibrous materials including wool, cotton, rayon, acetate, nylon and thelike textiles, or paper, leather, wood, felt and similar organic fibrousconstructions, and particularly cellulosic materials, by applying theselected quaternary ammonium derivatives, in aqueous medium butfered toabout pH 6 to the cloth, removing any excess, drying at a temperature inthe range of about 40 to 100 C., and heating the dry material to aboutto 140 C. for a period of the order of about .5 to 30 minutes to fix thefinish. Thereafter the material is desirably washed in a mildly alkalineaqueous solution to remove any residual acidic material, and dried.

D. The saturated alcohols are useful for the preparation of carbamatesby reaction with monoor poly-isocyanates.

In order more clearly to disclose the nature of the present invention, anumber of specific examples will now be described. It should beunderstood, however, that this is done solely by way of illustration andis intended neither to delineate the scope of the invention nor limitthe ambit of the appended claims. All parts are by weight in theexamples unless otherwise specified.

Example 1 The preparation of C F CH CHClCH OH from perfluorooctanesulfonyl chloride and allyl alcohol is given in Example 8a of U.S.Patent 2,965,659. 3-(perfluorooctyl)-propanol is prepared from thisadduct as follows: The adduct and approximately a four-fold molar excessof sodium hydroxide are dissolved in a solvent of equal parts of waterand ethanol and the solution is charged to a rocking high-pressurehydrogenation apparatus in the presence of Raney nickel catalyst.Hydrogenation is carried out at a temperature of about 130 C. with hydrogen supplied at 2500 p.s.i. pressure. The reduction mixture is filteredfree of the catalyst and the filtrate evaporated to remove the solvent.The residue is dissolved in ether and the ethereal solution washed withdilute hydrochloric acid and dried.

Vacuum distillation gives 3-(perfluorooctyl)-propanol, B.P. 112/910 mm.Hg.

S-(perfluorooctyl)-pentanol is prepared by reaction ofperfluorooctanesulfonyl chloride and penten-4-ol-1 in the presence ofditertiary butyl peroxide and subsequent catalytic dehydrohalogenation.

Example 2 The production of lO-chloro, 11-(perfiuorooctyl)-undecanoicacid and 2-chloro-3-(perfiuoroctyl)-propion.ic acid is described inExamples 2 and 11 of U.S. Patent 2,965,659. 4-chloro,S-(perfluorooctyl)-pentanoic acid is prepared in an analogous manner, asfollows:

A mixture of 26.8 g. (0.052 mole) of perfluorooctane sulfonyl chlorideand 5.0g. (0.050 mole) of 4-pentenoic acid (allylacetic acid) isrefluxed for four hours at about -145 C. in the presence of acatalyticamount (1.0 g.) of di-tertiary butyl peroxide. The reaction mixture isfractionally distilled under reduced pressure and the fraction boilingat about 100 C. at 0.01 mm. is collected. After recrystallization fromamixture of chloroform and carbon bisulfide, the4-chloro-5-(perfiuorooctyl)-pentanoic acid thus prepared melts at about8990 C.

The 4-chloro-5-(perfluorooctyl)-pentanoic acid thus prepared ishydrogenated by shaking a solution of 8.00 g.

(0.0145 mole) of the acid and 2.5 g. (0.062 mole) of sodium hydroxide ina mixture of 30 ml. of Water and .30 ml. ethanol for 3 hours at C. in arocking highpressure hydrogenation apparatus, in the presence of 4 g. ofRaney nickel catalyst and with hydrogen supplied at 2500 p.s.i.pressure. After removal of the catalyst and evaporation to dryness, anamorphous residue is obtained comprising sodiumS-(perfiuorooctyl)-pentanoate. By dissolving this residue in waterfollowed by acidification of the resulting solution,S-(perfluorooctyl)-pentanoic acid is recovered as a waxy white solid,which can be distilled at 100 C. at 0.02 mm. pressure. Afterrecrystallization from carbon bisulfide, the acid melts at about 86.5-87.3 C.

The procedure described in U.S. Patent 2,666,797, using lithium aluminumhydride, is employed for reduction of the acids to the correspondingalcohols. Thus, a suspension in ether of 30 parts of 5 (perfluorooctyl)pentanoic acid is added to a solution of 3 parts of lithium aluminumhydride in about 200 parts of anhydrous ether. The reaction mixture isstirred for about 48'hours and then is treated with water andneutralized with sulfuric acid. The reaction mixture is extractedseveral times with ether, and the ether extracts are combined, dried andfractionally distilled in vacuo. There is obtained 5-(perfiuorooctyl)-pentanol boiling at about 108 C. at 2.5 mm. Hg.

In the same way, using IO-undecenoic acid in preparation of theperfiuoro acid instead of allyl-acetic acid, there is produced1l-(perfiuorooctyl)-undecanoic acid, which on reduction yieldsll-(perfluorooctyl)-undecanol boiling at about 122126 C. at 0.10-0.15mm. Hg.

By repeating the foregoing procedure, employingperfluoro-n-pentanesulfonyl chloride and perfluorododecanesulfonylchloride (prepared by the process of Brice et al. as disclosed in U.S.Patent 2,732,398) instead of perfluorooctanesulfonyl chloride, there areobtained, respectively, S-(perfluoropentyl)-pentanoic acid "andS-(perfiuorododecyl)-pentanoic acid. Likewise, when 3-butenoic acid, 6-heptenoic acid and IO-undecenoic acid are employed instead of4-pentenoic acid in carrying out the procedure of this example, thereare obtained, respectively, the corresponding 4-(perfluorooctyl)-butyricacid, 7-(perfluorooctyl)-heptanoic acid and ll-(perfiuorooctyl)hendecanoic acid. Upon reduction, these acids yield the correspondingS-(perfluoropentyl)-pentanol, S-(perfluorododecyl)-pentanol,4-(perfluorooctyl)-butanol, 7-(perfiuorooctyl)-heptanol and1l-(perfluorooctyl)-hendecanol, respectively.

Example 3 The desulfonylative addition of a perfluoroalkane sulfonylchloride to an ester of an alkanol is disclosed in U.S. Patent2,965,659. An example is as follows:

To a mixture of 80 g. of perfluorooctane sulfonyl chloride and 31 g. ofallyl acetate are added about 3 g. of ditertiary butyl peroxide and thereaction mixture is slowly heated to about 80 C., whereupon aspontaneous rise in temperature to about 130 C. occurs. After thisreaction is over there is added a further amount of the di-tertiarybutyl peroxide. Heating is continued for about 14 hours at about 110 C.with a further addition of peroxide after about 8 hours of heating. Thereaction mixture is then fractionally distilled in vacuo, and the2-chloro-3-(perfiuorooctyl)propyl acetate which is formed in thereaction is recovered, as a fraction boiling at about 153158 C. at 37mm. pressure. To a solution of 50.5 g. of this substance in 50 ml. ofanhydrous methanol containing phenolphthalein indicator is addedslightly more than the theoretical amount of sodium methylate inmethanol solution. The reaction mixture becomes slightly pink and sodiumchloride is precipitated. After standing about 48 hours at roomtemperature, the reaction mixture is treated With about 10 ml. of waterand an additional amount of sodium methylate, and then warmed to about50 C. for about 4 hours. The organic phase is then removed andfractionally distilled, the fraction boiling over the range 129- 141 C.at 37 mm. pressure of mercury being recovered. The 3-(perfiuorooctyl)propen-2-o1-1 (i.e. 3-(perfluorooctyl) allyl alcohol) thus prepared hasindex of refraction n =l.3328. The boiling point of this alcohol is 62-65 C./0.08 mm. Hg.

A mixture of 42 g. of 3-(perfluorooctyl) allyl alcohol, 1.8 g. of Raneynickel, 45 ml. of ethanol and 1 g. of potassium hydroxide is charged toan autoclave and hydrogen under about 150 atmospheres pressure isintroduced. Hydrogenation to the corresponding saturated alcohol takesplace as evidenced by a drop in pressure over a period of about onehour. The contents of the autoclave are removed, filtered, and thefiltrate is fractionally distilled in vacuo. There is obtained3-(perfluorooctyl)- propanol, which boils at about l38143 C. at 38 mm.pressure and has index of refraction lz :1.33l2. The infra-redspectrogram of this substance indicates that it is completely saturated.

Alternatively, the chlorinated acetate adduct C F CH CHC1CH OCOCH can berefluxed in an inert solvent with a tertiary amine such as triethylamineto form the quaternary chloride salt. This salt can then be heated toeliminate triethylamine hydrochloride to form the unsaturated acetate.Similarly iodinated and brominated intermediate esters of the process ofthe invention can :be dehydrohalogenated to form the correspondingunsaturated esters. These umnsaturated esters can be hydrogenated andhydrolyzed to form the saturated alcohols.

Example 4 About 65.0 g. (0.125 m.) of C F So Cl, 23.5 g. (0.137 m.) ofCH =CH(CH OH and 0.2 g. of azobisisobutrylnitrile are heated withstirring to C. At that temperature, a rapid exotherm to 160 C. occurs,accompanied by an extremely rapid evolution of S0 After the reaction hassubsided, 2 ml. of di-ti-butylperoxide are added and the temperature ismaintained at 130-140 C. until gas evolution has ceased. The flask iscooled to 75 C. and evacuated to remove residual S0 To the crude adduct,C F CH CHCl(CH OH is added a solution of 14.0 :g. of KOH in 50 ml. ofabsolute ethanol. The mixture is stirred at 50 C. for 2 hours andallowed to stand at room temperature for 15 hours. The salts are removedby suction filtration, then the ethanol and water are distilled off at80 C. under vacuum (15 mm. Hg). The residue is taken up in ether, washedwith water and dried over MgSO Vacuum distillation gives 52.5 g. (71.5%)of a colorless liquid C F CH CH H (1l-(perfiuor-ooctyl)undecen-lO-ol-l)B.P. l21-125 C./ 0.08 mm. Hg; n :l.3770'.

In a similar manner 11(perfluorododecyl)-undecanol is prepared by thedehydrohalogenation of 10-bromo-11- (perfluorododecyl)undecylacetate(prepared according to the process of U.S. 2,965,659) to formll-perfluorododecyl-lO-undecen-l-ol which is in turn hydrogenated in anautoclave at high pressure and in the presence of Raney nickel to form11- (perfiuorodo decyl) -undecanol.

3-(perfluoropropyl)-propanol is prepared by the dehydrohalogenation of CF CH CHICH OH (which is prepared by reaction of pertfluor-opropyl iodidewith allyl alcohol) to form 2 Raney Nickel H: L Raney Nickel3-(per'fluoropropyl)-propanol is prepared starting with ethylperfi'uorobutyrate as flollows: Approximately equi- Inolar quantities ofethyl perfluorobutyrate, methyl acetate and sodium methoxide are used.The ethyl perfluoro- 10 anol is added to hydrolyze the complex. Thereaction mixture is next acidified with dilute sulfuric acid. The etherlayer is separated and the aqueous layer is further extracted with aboutan equal volume of ether. The combutyrate is added to a cooled solutionof sodium meth- 5 bined ether phases are evaporated to remove the etheroxide in absolute ether, with continued cooling. After and the residueis fractionally distilled- The 3-(heptastirring this mixture forapproximately two hours the i'luoropropyl) -pr-opanol thus obtainedboils at about 140- methyl acetate is added, whereupon aclear solutionforms. 141 C. at 745 mm. pressure and has index of refraction Thesolution is stirred for approximately 16 hours and n =1.3270. thenfractional'ly distilled under reduced pressure, to re- Example 6 g isolvenfs i to g i 'g gg g f g The alcohols are readily converted to the,correspond- Q E P EQ g 6 a g e .532 er ing acrylate and methacrylateesters by reacting them 18 pigena f pressure W1 may with acrylic acidand methacrylic acid or derivatives theremc cata'ifst, m et er 9 forabout {We of (e.g. acrylyl chloride and methacrylyl chloride) using Tcatalysf TemEWed 'fi'ltmnon and the filtrate i frac' conventionalesterification methods. The acrylate-type t1(many dimmed l'methylfidpcr' esters, i.e. monomers, shown in the following table are111101 P PYU- l Y propwnate 1S Tecovered, bol'llfl-g prepared in thismanner from the respective alcohols and at about 85 C. at 15 mm.pressure and having refractive acrylic acid or methacrylic acid exceptmonomer E which index n =1.35 13. About 157 parts of the hydroxy isprepared from the alcohol and methacrylyl chloride.

Monomer Monomer Characteristics Designation A 3-(perfiuorooctyD-propylacrylate Viscous, virtually colorless liquid 11.13 1.3421. Calculated:C, 31.5%; F, 60.6%. Found: 0, 31.3%; F, 59.9%. B11-(perfluorooctyl)-undecy1aerylate Solid, infrared spectrum showsexpected structure, melting point of about 28-36 C. C11-(perfiuorooctyD-undecyl methacrylate-. Tan, pasty solid melting atabout 2327 O. D S-(perfluoropropyl)-propylacrylate Boiling point -76/10mm., shows expected ilnggzged absorption maxima and has 71 of E 3-erfluoro r0 '1- r0 lmetha r late Boilin oint 70-73 0.10 mm., 121,1.3636. (p p py)p py fly Calclllti ted: C, 40.5%! F, 45.0%. Found:

0, 40.2%; F, 45.0%. F 5-(perfluoroocty1)-pcntylmethacrylata... Boilingpoint 102-104 0. /0.1 mm. Calculated: g,75.6%; F, 56.3%. Found: C,35.3%; F,

ester thus obtained and parts of phosphorus pe-ntoxide ,are mixed andallowed .to stand for approximately 16 hours (a rather strong exothermicreaction being noted shortly after mixing). The reaction mixture is thenfiltered and the filtrate is purified by fractional distillation. Thereis obtained methyl-3-(perfluoropropyl)acrylate which boils at 121-124"C. at 732 ml. pressure and has a refractive index n =l.3362. The acrylicester is hydrogenated in ether solution using Raney nickel catalyst andhigh pressure under the usual conditions. The reaction mixture isfiltered and the filtrate is fractionally distilled under reducedpressure. There is obtained the corresponding saturated ester, met-hylB-(perfiuoropnopyl) pr-opionate, which boils at 42 C. at 12 mm. pressureand has refractive index n =1.3276. To a solution of 7.6 g. (0.2 mole)or lithium aluminum hydride in 500 ml. of ether are added 49 g. (0.191mole) of the methyl-3-(perfiuoropropyl) propionate dissolved in 100 ml.of ether, at such a rate that vigorous refluxing is maintained. Themixture is then stirred for 1 hour and an excess of meth- Theseacrylate-type monomers are readily polymerized by methods known to theart, for example, by bulk polymerization, solution polymerization andemulsion polymerization, using catalysts such as benzoyl peroxide orother free radical polymerization initiators. Thus, monomer A is bulkpolymerized by adding 0.5% of benzoyl peroxide to the monomer andheating at 50 C. for 2.5 hours to form a rather tough rubber.

Monomers A through F are emulsion polymerized, the procedure and theamounts of ingredients employed being as follows except as otherwisespecified:

A suitable vessel is charged, frozen in liquid air, evacuated to apressure of less than 0.01 mm. of mercury, thawed and refrozen,reevacuated and finally sealed. The vessel is then agitated in a 50 C.water bath for from about 15 to 18 hours. The charge, except Whereotherwise specified, is 100 parts by weight of monomer, 5 parts ofemulsifier, /2 part of potassium persulfate and parts of medium. Theresults of these various runs are summarized in the following table:

Emulsi- Conversion Monomer fier Medium amt. latex, Remarks (1,) Polymerpercent Water 108, Methanol 72 68 Clear, blue latex contg. noprecoagulum 0.35 I.

( Water 128, Acetone 54 Blue, slightly cloudy, trace of precoagulum 0.40 II.

d0 Sliggtly tan, some precoagulum 11 0. 14 III. 0

( Water 180.

( do Bluish latex Watgr 126, Acetone 54- Clear, blue latex- Water 180Water 126, Acetone 54 1 Potassium 1l-perfluorooetylhendecanoate.

2 Inherent viscosity in 1:2 acetone-methyl perfiuorobutyrate. 3Potassium N-ethyl-2-(perfluorooctanesulionamido)acetate.

4 Sodium lauryl sulfate,

5 3.2 parts of emulsifier and part of potassium persuliate used.Reaction time 5 hours.

Latex then frozen to coagulate.

11 Polymerization carried out in an atmosphere of nitrogen.

Certain of these latexes (emulsions) are applied to various types ofcloth and the treated cloths tested for waterand oil-repellency. Thetest procedures used, except where otherwise specified are as follows: Aseven by seven inch square of test cloth is treated by padding thereonthe emulsion diluted to 1% solids with water so that about 1% of polymer(based on fabric weight) is present in the fabric. The treated fabric isthen dried minutes at 140 C. and tested for resistance to water and oil.

Hydrophobic properties of the treated cloth are determined by Method22-52 of the American Association of Textile Chemists and Colorists asdescribed, for example, on pages 136 to 138, inclusive, of the TechnicalManual and Yearbook of that association for the year 1954. It is to benoted that this method provides for no interpolation of results whichare reported as one of the Standard Spray Test ratings 0, 50, 70, 80, 90and 100.

Oleophobic properties are measured by means of ratings assigned on thebasis of resistance for 3 minutes to drops of oil-turpentine mixturesvarying by 10% incremediately for resistance to oil and water, thesecond group is immersed in anhydrous hydrazine at C. for 2 /2 minutes,washed with water and dried for 4 minutes at 150 C. before being testedfor resistance to water and oil and the third group is immersed in 10%aqueous sodium hydroxide at 75 C. for 2 /2 minutes, washed with waterand dried for 4 minutes at 150 C. before being tested for resistance tooil and water. The oil repellency rating test used is that described inFootnote 4 of the previous table and the ink resistance test is asfollows:

A drop of ink is dropped on the treated fabric from a height of 2 inchesand the drop is immediately removed by blotting with an absorbenttissue. A cloth sample in which there is no staining or a very faintstaining at the point of impact is rated good, a sample in which a clearimprint of the whole drop of ink remains is rated fair," a sample inwhich the ink color appears to have spread slightly from the originaloutline of the drop is rated poor and a sample in which the drop of inkhas soaked into the fabric before the blotting is rated NR. (NoResistance). The results of these tests are as folments from puremineral oil (Nujol, Stanolind, etc.) to IOWSI Initial Hydrazino SodiumHydroxide Latex Cloth Oil Ink Oil Ink Oil Ink XI Cotton print cloth 100+Good 80 Go od 80+ Good. XI Cotton gingham 100-l- ..d0 70--- Fair 60 Do.XI Cottontwill 110+ do 100+ Good 100 Do.

pure turpentine applied gently to the surface of the textile held in ahorizontal position. The rating given corresponds to the test mixture ofthe highest turpentine content repelled. Thus, 10 indicates that amixture of 0% oil-100% turpentine fails'to penetrate the cloth within 3minutes; the rating 1 indicates that a mxiture of 90% oil-10% turpentinefails to penetrate the cloth within 3 minutes, etc.

The results are as follows:

Visa is the tradename of Deering-Millikcn and 00., Inc. for a fabricgtgisisting of a blend of 45% wool and 55% polyethylene terephthalate 1ers.

2 Properties not lost on repeated dry cleaning.

3 Significant.

4 Oil repellency ratings based on failure of penetration of mixtures ofmineral oil (Nujol) and n-hcptanc for 3 minutes. The ratingscorresponding to the highest percentages (by volume) of hcptane repelledare: no hold out to mineral oil, 0; 0% heptane, 50; 20% heptanc, 70;hep- Eane, heptane, 90; licptane, 100; heptane, 110; 70% hepane, 0.

Additional cloth treatment tests are carried out utilizing latex XI asfollows: The latex is diluted with water to approximately 1% solids anda number of samples of cotton print cloth, cotton gingham and cottontwill are immersed therein. The cloth samples are then removed, runbetween nip rolls to remove the excess treating bath and dried for 10minutes at 140-150 C. The dried treated cloth samples contain about 1%of polymer (based on the fabric weight). The treated samples are thendivided into three groups. The first group is tested im- The foregoingtable shows the excellent resistance to bases of these treatments. Theresistance to base hydrolysis of these polymers can be tested directlyas follows: The ampoule in which the latex is prepared is opened and anequal volume of 28 percent aqueous ammonia is added. The ampoule isrescaled, rotated end over end for 18 hours at 50 C., opened tand thelatex coagulated by pouring it into acetone. The polymeric material isrecovered, washed and dried and analyzed for nitrogen. A very lownitrogen content indicates a high degree of resistance to ammonolysis(alkaline hydrolysis) while higher nitrogen content indicates a lowerresistance to ammonolysis. Latexes IX and X are found to have excellentresistance to base hydrolysis according to this test (nitogren contentsof 0.08 and 0.15 wt. percent respectively determined according to thetest).

The white, rubbery coagulated latex V is separated, washed and dried andis found to have an inherent viscosity in 2:1acetone:methylperfluorobutyrate of 2.3. The rubber is cured by blendingparts of polymer with 6.72 parts of sodium silicate nonahydrate and 2.72parts calcium hydroxide followed by heating at 310 C. in a press at 900pounds pressure for 20 hours. A rubbery elastomer showing goodresistance to oils is obtained, which, when prepared in sheet form, isuseful for preparing gaskets, ca-p liners and the like.

The cured rubber shows a flexing resistance tenfold that at roomtemperature (T of 11 as determined by ASTM Procedure D 3-54T. It istested for solvent resistance by ASTM Procedure D471-54T and shows thefollowing:

Tensile strength and elasticity are measured by the usual stretchingmethods. There is 100% elongation at 361 pounds per square inchcross-section and 200% at 470 p.s.i. Break occurs at 482 p.s.i. at whichpoint there is 260% elongation and a permanent deformation of 18%.

13 Example 7 Among the fiuorochemical triazines which can be preparedirom the alcohols are:

2,4-diamino-6- w-perfiuorooctylundecyloxy) -s-triazine;

2,4-diamino-6- w-perfiuoropropylpropyloxy) -s-triazine;

2,4-diamino-6-(w-perfiuorododecyldodecyloxy)-s-triazine2,4-dihydrazino-6-(w-perfluoropropylpropyloxy)-striazine;

2,4-diamino-6- w-perflu-orooctylpropyloxy) -s-triazine;

2,4-dihydrazino-6- (w-perfiuorododecyldodecyloxy) -striazine; etc.

Quaternizlng Salt Alcohol Agent Quaternary Salt Remarks re theQuaternary Salt Detsiigna on C Fi7(CHz) OH Pyrldme C&F17(CH2)5OGHIN 01-Solid; Analytical: Cale. N, 2.21%. Found N, 2.20%.- A.

t CaF1 (CH )11OH d C8F17(CH2)11OCH2N C1- Whlte crystals, M.P. about 780.; Analytical: Cale. B.

N, 1.95%. Found N, 1.99%. CKF1 (CH1)11OH Triethylaminen[CsFiKCHzlnOCHzN(CgH )a] Cl Solid; M.P. 85 C. upward; Analytical: Cale.N, C.

1.90%, C, 42.4%; F, 43.6%. Found N, 2.04%, o, 42.4%; F, 38.1%.

CgF11-(CH2)11OH QLllIlOllIlE CKF17(CH3)11OCH2N Cl Solid, M.P.120125 0.;Analytical: Cale. N, 1.83%, D.

\ 1 o, F, 42.1%. Found N, 2.08%, o, 46.2%, a.

CgF17(CH:5)l1OH Pyridine OiFi1(CH:)uOCHN Br- Solid, softens at about 900.; Analytical: Calc. (for E.

\ monohydrate) N, 1.84%, C, 39.4%, Br, 10.5%.

Found N, 2.3%, O, 39.2%, Br, 13.7%.

1 Anhydrous hydrogen bromide gas is used in place of hydrogen chloride.

These and the other triazines have the general formula:

wherein R m, X and Y are as previously defined herein. These compoundsare valuable curing agents for epoxytype resins (such as the bis phenolA-epichlorohydrin resin available commercially under the tradedesignation Epon 828) and thus provide a novel method of introducingchemically bound perfiuoroalkyl groups into epoxy resins.

The condensation products of the triazines with formaldehyde also impartdesirable hydrophobic and oleo-phobic properties to textiles such ascotton, wool, linen, silk and synthetic fibers as Well as to non-wovenmats or webs of fibers such as paper and felt. Thus, for example, theresin produced by refluxing together for from about 1 to 4 hours atriazine of the type defined by the foregoing general formula andconcentrated aqueous formaldehyde can be dissolved in a suitablesolvent, e.g. dioxane, in a concentration of about 1% and utilized toimpregnate cotton cloth. The impregnated cloth can then be dried toremove the solvent and heated for five minutes or more at a temperatureof from about 120 to 180 C. The resulting treated cloth samples arehighly resistant to both oil and water type stains and retain theirresistance to these stains to a remarkable degree even after repeatedlaundering.

Another use for the compounds of the invention and more particularly fortheir formaldehyde condensates is as hardening agents foralkyl-urea-formaldehyde, and

melamine-formaldehyde resins. A simultaneous increase in the oilandwater-repellency of the surfaces of the resins so hardened is producedbecause of the fluorochemical chain introduced and chemically boundtherein.

Example 8 Several quaternary amine salt derivatives of the saturatedalcohols are prepared as follows, except as other- Soil-resistant,waterand oil-repellent cloth is produced using these quaternary salts(and similar salts prepared from the other alcohols of the invention asfollows:

The treating solution is prepared by warming sodium acetate trihydrateand the selected treating agent in water at the desired concentrations,which can range from about 0.1 to about 5%, at about 30 to 40 C. untilsolution is effected. The cloth to be treated is soaked in this solutionfor one minute, removed and squeezed so that a weight of solutionapproximately equal to 75 to of the Weight of the cloth is retained.Under these conditions, the preferred concentration of treating solutionranges from about 0.5 to about 2%. The cloth is then dried for about 10to 30 minutes at 40 to 100 C. and the treatment is fixed by heating thecloth for about 5 to 30 minutes at from about 100 to 140 C. The fixed,treated cloth is washed for about 30 minutes in an aqueous solutioncontaining 0.1% w./v. of sodium lauryl sulfate and 0.2% w./v. sodiumcarbonate, at about 50 to 60 C., rinsed thoroughly and again dried.

The effectiveness of the treatments is determined by means of tests forspray rating, oil repellency rating and the visual estimation of soilrepellency both before fur- .ther treatment and after one or more cyclesof laundering and/ or dry cleaning.

For test purposes, laundering is accomplished by Washing in an automaticwashing machine of the stationary type using a detergent under normalhousehold procedures or by means of a standard 60 minute cycle in aLaunder- O-Meter, using chip soap as specified in ASTM D-496.Dry-cleaning is performed by available commercial procedures employing,for example, perfluoroethylene or naphtha.

Treating solutions are prepared as described above by warming one partof sodium acetate trihydrate and two parts of the quaternary salt in 100parts of water. Samples of cotton jeans cloth are treated with therespective solutions, dried at 100 C. for 30 minutes, heated for 5minutes at C. (except for sample B which is heated for 5 minutes at 121C.), Washed and dried as described above and rated as follows (the SprayRating being as previously disclosed herein and the Oil Repellency beingthe previously described mineral oil-n-heptane test):

Salt Designation Oil Spray Percent F Repellency Rating on Fabric B 80 900.9 C 50+ 80 0.23 D 70 80 E 100 70 0.5

1 Not determined.

All show appreciable soil resistance and retain appreciable percentageof oiland water-repellency after laundering or dry-cleaning.Substantially the same resutls are observed when nylon and woolenfabrics are similarly treated.

Example 9 Diurethanes, which are useful in the treatment of textilefabrics, can be prepared by the reaction of the saturated alcohols withdiisocyanates. The following is exemplary of this:

0.665 g. (.0014 mole) of 3-(perfluor0octyl)-propanol and 2.177 g. oftoluene are added to a vial, the vial is warmed until solution hasoccurred and 0.1218 g. (.0007 mole) of toluene diisocyanate are added. Atrace of phenyl mercury acetate is added as a catalyst. The vial issealed and heated at 65 C. for one hour, 105 C. for 2 hours and 14 hoursat 65 C. Solution is complete throughout the entire heating period. Thereaction mixture is cooled and the product diurethane forms a lowerlayer in the toluene. The toluene is removed by evaporation under vacuumleaving a clear solid melting at about 50-55 C.

A 1 percent solution of the diurethane in a 10/90acetone/1,1,1-trichloroethane mixture is padded onto various textilefabrics which are then nipped, air dried overnight and tested with thefollowing results:

Fabric Oil Repellency Spray Rating 2 Rating 1 Cotton fabric 140 Woolgabardine 150 Nylon 70 Viscose rayon 50 2.3-(perfiu0rooctyl)propene-2-ol-1. 3. 11-(perfluorooctyl)undecen-lO-ol-l.

References Cited by the Examiner UNITED STATES PATENTS 2,561,516 7/1951Ladd et al 260-988 2,666,797 1/1954 Hunted et al 260-633 2,950,3178/1960 Brown et a1. 260-633 2,965,659 12/ 1960 Tiers.

3,145,222 8/1964 Brace 260-633 LEON ZITVER, Primary Examiner.

I. E. EVANS, Assistant Examiner.

1. A FLUORINATED ALCOHOL OF THE FORMULA: